Chlorination apparatus



De c-. 1, 1925- 3 Sheets-Sheet 1 5. BROWN CHLORINATION APPARATUS Flled Jan 13, 1921 Deco 1, 1925- 1,564,044

8. BROWN CHLORINATION APPARATUS Filed Jan. 13, 1921 3 Sheets-Sheet 2 Dec. 1, 1925- 8. BROWN CHLORINATION APPARATUS F iled Jan. 13, 1921 s Sheets-Sheet 5 To all whom it may concern:

Be it known that I, SANDFORD BROWN, :1

Patented Dec. 1, UNITED STATES 1,564,044 FATE smronn BROWN, or NEWARK, new JERSEY, .ASSIGNOR, BY'MESNE nssmnmnnrs, TO HALOWAX CORPORATION, or NEW 11031:, N. Y., A CORPORATION or New YORK.

GELORINATION APPARATUS.

Application filed January 13, 1921. Serial No. 437,010.

citizen of the United States, residing at New ark, in the county of Essex and State of New ew and use-' Jersey, have invented certain ful Improvements in Chlorination 'Appa; ratus, of which the following is a specification. 1

My invention relates to a process for chlorinating organic aromatic hydrocarbon materials, particularly naphthalene, and recovering hydrochloric acid evolved during the chlorination process. My invention also relates to improved apparatus which may be used in carrying out the process referred to.

Naphthaline may be chlorinated bymaintaining bodies of thesame in molten condition in a series of pots orchlorinating vessels through which chlorine gas is successively passed. In all the prior practices with which I am familiar it has been deemed necessary, or highly advantageous, to maintain the naphthalene -or organic material which is to be chlorinated, under pressure, and to force the chlorine gas through the material. It has been stated that the ra idity of absorption of'the chlorineby napht alene 'or other hydro-carbon will be increased when the temperature and pressure are raised above 212 F. and atmospheric pressure respectively.

I have found on the contrary that the chlorination proceeds as eifectively when a partial vacuum is maintained in the ClllOIlnating chamber, that is, a pressure less than atmospheric, the chlorine gas being drawn through the chlorinatin chambers by suction instead of being gorced through the same, the chlorinating chambers being heated in. the usual way, as by.means of steam jackets.

An important advantage of this procedure is that there can be no leakage from the chlorinating apparatus into the atmosphere,

surrounding the same. In the previous practice, in which pressures up to fifty pounds per square inch were used in the chlorinating vessels, leakage from the system was frequent and this was highly dangerous and costly as both chlorine and hydrochloric acid (which is produced in the course of the process) escape and affect the workmen and surrounding property; this is particularly true of the hydrochloric acid gas which combining with the moisture of the atmosphere to form hydrochloric acid NT orr'lcs.

solution is very destructive of apparatus,

piping, roofing, etc. Accordingly, it was customaryto carry out .the reaction out of doors. W th my present method-there can be no leakage outward from either the chlorinating vesselor the hydrochloric recovery vessels; the latter are usually located'outdoors because ofleakage; in fact, a..usual part of the system is a ilarge' and costlytower ventilated to the open air. 4

It is essential that-the chlorinating vessels be i'nstalled inside of the building forefii cient and ponveni'ent' operation, to, prevent I radiation losses and to permit easy handling of theproduct, and it is very advantageous also for it to be possible tooperate the hydrochloric vessels within the buildin thus preventing damage by freezing. M system makes the operation of both the chlorinating and. acid vessels indoors quite practical, as the leaks are. always ofair into the system and not of deleterious gases out of the system, and these leaks may be readily detected by hissing sounds at .the point of leakage or by the pressure difference on the gauges.

. When leaksarise in the chlorinating vessels, as ordinarily operated, the operation must be stopped immediately until re airs are made, whereas in my system, the eaks may be detected and easily repaired without stopping the operation.

A further and important advantage of the suction and vacuum method referred to relates to the method of acid absorption which may be utilized. In the prior practice, chlorine gas being positively pumped through the chlorinating vessels, the hydrochloric acid gas evolved was progressed under slight pressure through a series of absorbing vessels containing water, known as tourills containing water, and the usual absorption towers. With this system the hythe prior installations being actually very slight. When, however, for any reason con-' large number of absorbers is necessary. The

area of the aqueous absorbing surface for each umt of volume of gas passing over it, must be very large, necessitating a large volume of liquid.

This difficulty is overcome by my method whereby the entire system is maintained under a partial vacuum, thechlorine gas betinuous touril ing medium, the velocity of the ing sucked through the chlorinating vessels and the hydrochloric acid gas being sucked through the'absorption system, in a conrocess. Because of this modification of t e process, it is possible to introduce hydrochloric acid gas near the bottom of each tourill and have the same bubble up through the entire body of water in each the suction being sufiicient to permit theuse of this method. Because of this procedure theacid is absorbed much more effectively and economically than in the previous method, the number of tourills required being only a small fraction of the number required in the previous system, and no large absorbing towers being required. There is accordingly a considerable saving of floor space and expense for plant, with added eiiiciency absorption, greater safety and other desirable features. In my system, all the gas comes into positive contact with the absorb- I gas may be relatively high and the volume 0 unit of volume of gas may be relatively small.

It is also advantageous in many cases to operate several chlorinating and acid recovery systems in parallel as will be more fully explained hereinafter.

The objects of my invention relate to an improved process in accordance with the foregoing, and suitable apparatus by which the process may be carried out.

In order that my invention may be more clearl. understood, attention is hereby directe to the accompanying drawings forming part of this application and illustrating one manner of practicing my improved process, and one form of apparatus in which the same may be carried out. In the drawings Fig. 1 represents diagrammatically a side elevation of apparatus comprising a chlorinating and acid absorbing installation; Fig. 2 is a diagrammatic top plan view of the same; Fig. 3 is an enlarged vertical section taken through the adjacent portions of a pair of chlorinating pots; Fig. 4 is a view partly in side elevation and partly in ver water per tical section of a pair of ad'acent tourills or acid absorbing vessels an Fig. 5 is a diagrammatic top plan view of a modified form of apparatus, embodying parallel chlorinating and acid recovery systems.

Referring to the drawings I have illus-' trated a series ofthree chlorinating pots 1, 2 and 3, it being understood that any desired number may be used. These pots are re resented as being similar to those describe in Patent 1,294,230 granted to Kirk Brown February 11, 1919.

These pots are suitably heated preferably by steam jacketing the same on the bottoms and about their sides as is indicated at 4 and 5. Naphthalene or other material to be chlorinated is led into the system, preferably from one end until the same extends in fluid condition at a desired level in all the pots, after which chlorine as may be introduced into the system, at t e other end. In the drawings I have diagrammatically indicated a tank I 6 from which naphthalene flows through a pipe 7 provided with a valve 8 into the pot 3. At the opposite end of the series 0 chlorinating vessels I have indicated a pipe 9', provided with a shut-oil valve 9", through which chlorine may be introduced below the surface of the naphthalene in 0t 1. These pots are kept closed during t e chlorinating operation and may.

be provided with covers 10 secured in any desired manner.

The chlorine gas is drawn through the system by means of a pump indicated at 11. The connection between each pair of chlorinating pots such as 1, 2 and 3 is preferably made in the manner described in Patent 1,294,230 referred to, my invention, however, not being limited to such an arrangement. As shown a pipe 12 is provided in each pot. As is shown in Fig. 3, each pipe 12 is connected by a coupling 13 with a corresponding pipe section 12 in the adjacent pot, section 12 being connected by an elbow 14 with a vertical pipe 15 provided with a valve seat at its upper end, above the normal level of the naphthalene. A valve is provided having a part 16 to coact with this valve seat and to control the opening in the top of the pipe 15. This valve is operated from the exterior of the pot, as by means of valve stem 17 operated by a hand wheel 18. I

The pots are provided with a series of superposed pans 19 as is usual in a chlorinating apparatus. The chlorine gas which enters pot 1 through pipe 9 is drawn by the suction of pump 11 through the naphthalene in pot 1, some of the chlorine gas, together with hydrochloric acid as, which is evolved in the chlorination of t 1e naphthalene passing through the valve and 'pipe connections to pot 2, and some of the chlorine gas and a greater quantity of hydrochloric acid gas passing through the valve and pipe connections in pot 2 into pot 3. When the material in pot'l has been chlorinated to a desired stage the supply of chlorine gas passing through pipe 9 may be stopped, the valve in pot 1 closed and the chlorinated product removed from-pot 1, after which the partially chlorinated product in pots 2 and '3 may be blown over or otherwise transferred to pots 1 and 2, and pot 3 refilled with naphthalene to be chlorinated, after which the operation may be repeated.

Hydrochloric acid gas evolved in the chlorination passes from pot 3 through a series of tourills, at the end of which the pump 11 is connected. In the construction shown the hydrothloric acid gas passes from pot 3 through a pipe connection 19' to a tourill 20. From this point the acid gas,

which has not been absorbed within the water in tourill 20 may pass through pipe connection 21 to a tourlll 22 and thence through tourills 23 and 24 which are connected in series by connections 25 and 26. Or, the gas may pass through connection 21' to a tourill 22 and'thence through tourills 23 and 24' whichare similarly connected in series. Pipe connections 21 and 21 are provided with suitable valves 27, 27' so that one series or the otherof tourills, or both series in parallel, may be utilized. From the last tourill of either series 24 or 24', any acid gas which has not been absorbed will pass through connection 28 or 28 to a tourill 29 which is connected by connection 30 to thepump. 7

The acid absorbing vessels are preferably stoneware tourills as shown which are filled to a suitable level with water. The gas entering any one of the same, such as the tourill 20, passes downwardly therein through a perforated p1 31 from which; the gas passes within t e water and bubbles up. through the same, a part of the gas being absorbed. Any gas which passes over will pass in like manner through the various tourills of the series until the same is all absorbed. When the acid solution is to be removed from one series of tourills such as 22,23 and 24, valve 27 may be closed and.

valve 27 opened so that the gas will then pass through the other series. The tourills are kept closed during the operation of the system and may be provided with valved i to ' from anyof the pots'l, 2 or 3 in any desired manner as by drawing the same off through connection 33'.

a The lasttouri1l29 which is directly connected with the pump may be used as an indicator- In the normal operation of the system no gas should come over into this horizontal arm of bell-crank 36. A similar tourill, but all of the same should be absorbed within the preceding tourills.

It will be seen that in the operation of the system the pump 11 exerts a continuous suction upon all of the chlorinating pots and the acid absorbing vessels which 'are connected therewith in series and produces a partial vacuum in all of the same.

At various points of the gas passage throughout the system safety valves should beloo ated to prevent the liquids from backing dver into the preceding vessels in the event of stoppage of the pump or a serious break in the vacuum. These safety valves are so designed that the vacuum will be re- 90 leased on the inlet to the vessels before the v liquids can back up through the outlet. This effect is obtained by bringing the liquids'to a state of hydrostatic balance.

A safety valve is indicated in Fig. 1 in the inlet pipe 9, in which plate 34 covers outlet'35 of the pipe, plate 34 being mounted on a bell-crank 36 pivoted at 37 to the strap 38; A, counterweight 39 is carried by the valve is 'located'between the acid recovery and chlorinating units on the downwardly extending portion 40 of'connection 19, the plate 34' being mounted in the same manner as plate 34 described above. If a break in the line occurs at any pointbetween valve 9' and pump 11 the safety valves will open, thus reventing the liquids in the system from aoking over,into the preceding vessels. I

An arrangement of both chlorinatin and acid absorbin vessels in parallel trains is indicated in ig. 5, in whlch entrance pipe 9 for the chlorine connects through pipe 41 toa train of chlorinating vessels 1, 2 3*, or 105 throu h pi e 42 to chlorinating vessels 1 2? an 3, t ese being similar in all respects to the vessels 1, 2, 3, andtheir connections, previously described. Connection may be made for the acid gas to pass from vessel 3 to the tourills 22, 23 and 24, and from. vessel 3 to tourills 22", 23 and 24 connection being made from vessels 24 and 24 re spectively through pipes 28 and 28 to the P mp Since the resistance oifered to the passa e of the gas throu h the system varies direct y as the sum of t e hydrostatic heads of the liquid \in' the various .vessels, it is obvious that any number of chlorinating and absorb- 9 ing units may be operated in parallel simultaneously by ongvpump without increasing the resistance. en 0 crating in parallel,

the flow of gas throug the various units which there is the least resistance. As the chlorination proceeds, the liquids will increase in specific gravity and 'consetilllently By operating several systemsin para1lel,- the production process is greatly'facilitated,

for when the contents'of anyone unit have reached the desired degreeof concentration, the unit ma be cut out of the system, the contents withdrawn, and the unit recharged without stopping the operation of'the balance of the system.- In re ard to the system generally, it. may

be noted that the pumps available for forcing chlorine gas under positive pressure are very unsatisfactory, it beingjnecessary even with the best "of them, to replace the packing frequently due to the corrosion from the as and sulphuric acid which is used in conunction w th them; 7

In my system, the pump sufi'ers no-abnormal depreciation, since it"merely maintains a static balance 'at the end of the system, there being no gas "passed through it whatever. 1

- By permitting the first absorption vessels or vessel, such as 20, of the acid system to remain in a completely concentrated state, and using it as a washer, a particularly fine ,form of acid may nated in lhpiiid' form,

a suction pump be procured in the balance of the absorption system.

- What I claim is:

1. In chlorine-utilizing combination of a lurality of series of normally closed vessels adaptedfor the chlorination of naphthalene, in parallel, means for introducing therein material to be chlorimeans for connecting at will the rst vessel of'eith'er series, or ofboth series, to, a chlorine gascontainer," and.

connected to the last vessel apparatus, the

of each series.- a

2. In chlorine-utilizing apparatus, the combination of a plurality of trains of normally closed chlorinating vessels, said trains" being connected:in parallel and the units of each train being connected together in series, means for introducing therein mate- "rial to be chlorinated in liquid form,mean's for connecting at will the first vessel of either train-or of both trains to a chlorine gas container a plurality, equal to said first 'namedplura ity, oftrains of tourills contourill of each train.

This specification signed this 7th day of- January, 1921. r

1 SANDFORD BROWN. 

